TW307789B - - Google Patents

Description

A6 307789 _B6_ V. Description of the invention (3) (Please read the precautions on page f before filling out this page) The invention of the Eu city case application is the US application case No. 928, 8 7 8 (August 1992) On the 12th, the application was filed. The invention is related to a polymer containing a high percentage of vinyl alcohol units blended with certain alkyl methacrylates and / or alkyl acrylates and unsaturated organic acids (such as methacrylic acid) and / or vinyl amide structures ( Such as N-vinylpyrrolidone) melt-processable cooked plastic composition, and then the compound is blended with one or more polar polymers (or three polymers at the same time); polar polymers such as polyester, such as poly ( Ethylene terephthalate), poly (vinyl chloride), polyurethane, such as thermoplastic polyurethane, polyamide, polyester, ethylene-vinyl alcohol copolymer and terpolymer, polyglutarate Amine, methyl methacrylate polymers and copolymers, polymers of natural origin such as starch, chitin, chitosan, lignin or cellulose. Such blends can be processed by conventional plastic technology to form sheets, extruded or blown films, molded objects, etc. It can exhibit a balance of shielding and strength properties, such as good resistance to gas penetration, low Moisture absorption, and firmness / modulus balance suitable for packaging applications. Invented the reticle of the Ministry of Economic Affairs of the Ministry of Economic Affairs, printing all materials that synthetic polymers believe to have useful gas permeability properties, such as resistance to gas, disulfide, water, etc .; poly (vinyl alcohol ) (PV0H) A polymer composed of the following structural units: -CH2-CH-

I 0H, and it is prepared by the complete or almost complete hydrolysis of homopolymer of vinyl acetate or related vinyl ester; the starting polymer prepared by the structural unit of the following formula: ) A 4 specifications (210 X 297 mm) 3 82. 9. 6,000 307789 Central Standards Bureau of the Ministry of Economic Affairs of the Ministry of Industry and Fisheries Co-printed A6 B6 V. Description of invention (4) -C Η 2-C Η-

I

OOCR (where R is an alkyl group, ie an alkyl group of 1 to 8 atoms, preferably a methyl group) is the least permeable to the passage of small molecules, PV0H is derived from the high cohesive energy density and the polarity of the hydroxyl group This property, the presence of a hydroxyl network, has the coexistence effect that gives the polymer (PV0H) gas impermeability but is sensitive to moisture, due to the high polarity of the 0H functional group; ^ strong intermolecular interactions can improve PV0H degradation The melting temperature near the temperature, therefore, accompanied by the degradation of the melting system, the degradation is too heavy, the PV0H itself cannot be melt extruded or injection molded. Copolymers with a low percentage of ethylene moles, such as about 5 to about 25 mole%, are similar to poly (vinyl alcohol). Without plasticizer auxiliary ribs, they cannot be melt processed into films. In the US Patent Application No. 07 / 781,715 filed on October 22, 1991, it is also the European Patent Application No. 91-311265 of the applicant on December 4, 1991 (some inventors are the same as this case). Additive polymers for melt processing of the above poly (vinyl alcohol) materials without changing their physical and shielding properties. These additive polymers are copolymers of methacrylic acid or lower alkyl esters of acrylic acid with various nitrogen-containing monomers , Especially those with an amide group, and most particularly N-vinylpyrrolidone. It also shows more useful additive terpolymers containing lower alkyl esters of methacrylic acid or acrylic acid, the same nitrogen-containing comonomer, and copolymerized unsaturated carboxylic acid (such as methacrylic acid). It also shows that these latter terpolymers can form a segmented copolymer when combined with a poly (vinyl alcohol) matrix polymer under certain processing conditions. In the US Patent Application No. 872478 filed on April 23, 1992 (some inventors are also the same as this case), it is indicated that the methacrylic acid and / or C-copy paper size is in accordance with the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) 4 82. 9. 6,000 ------------ f ---------- installed --------, -------- line (Please read the precautions on the back before filling in this page) A6 B6 printed by R Industry and Consumer Cooperative of Central Bureau of Standards of the Ministry of Economy V. Description of invention (5) Copolymer of lower alkyl enoate and unsaturated carboxylic acid, such as A The copolymer of methyl acrylate and methacrylic acid can also be used for the same purpose. It also shows that the resulting composite can be a segmented copolymer under certain processing conditions.

The present invention found that certain poly (vinyl alcohol), or copolymers containing at least 50 mole% of -CH2-CH- units and having at least one copolymerizable acid or amide 0H, especially cyclic enzymes, can Compounds of low methacrylic acid or lower alkyl esters of acrylic acid, when melt-blended with structural polar polymers, can produce blends with excellent physical, optical, and masking properties. In the above application, it was found that a polymer composite comprising about 40 to about 95 parts of the first polymer and about 5 to about 60 parts by weight of the second polymer can be melt processed, such as extruded into useful targets such as tablets Articles, films and fibers; the first polymer contains at least 50 mol%, preferably at least 90 mol% of -CH2-CH- structural units and any -CH2-CHR- (where R is Η or CH3)

I 0Η structural unit; the second polymer contains at least 70 parts of units derived from at least one methacrylic acid or lower alkyl ester of acrylic acid, preferably methyl methacrylate, and at least one part derived from about 25 parts Contains an amide group, preferably a cyclic amide group structure of -C Η 2-ρ Η-(where η is 2, 3, 4 or 5)

W

(C Η 2) n-C = 0 units, preferably vinyl or vinylidene monomers derived from units of N-vinylpyrrole copper, or up to about 25 parts derived from unsaturated carboxylic acids or anhydrides, It is a unit of methacrylic acid. And further found that by melt blending the above two paper standards are applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 gong)) 5 82. 9. 6,000 -------------.- --- η, ------- install ------, -------- recognize-. ^. (Please read the notes on the back before writing this page) A6 B6 307789 V. Invention Instructions (6) (Please read the precautions on the back before writing this page) The combination of polymers will form a segmented melt processable polymer in which two polymers are chemically combined to form a graft copolymer. When the additive polymer does not contain aldolamine functionality, or when the compound contains poly (vinyl alcohol) that has been washed or neutralized with an acid (such as phosphoric acid) to remove residual sodium acetate, it can be used in the compound. Additives (as low as 2 parts), as taught in US Patent No. 3,425, 9 7 9. It has been found that these compounds are preferably blended in a molten state with polar polymers to obtain melt-processable blends that can be processed into useful sheets, films, or molding targets; strictly speaking, polar The processing of polymers can be improved, so these compounds can be considered as a processing aid. Polar polymers can be described as polymers containing functionalities other than hydrogen and hydrogen, and contain poly (ethylene halides), such as poly ( Argon ethylene) (PVC); poly (vinyl ester), such as poly (vinyl acetate), poly (meth) acrylate, polyglutarimide; polymers containing (meth) acrylonitrile, such as styrene / Acrylonitrile copolymer or acrylonitrile / butadiene / styrene copolymer (ABS); polyesters, such as poly (alkyl terephthalate), polyaldehyde amine, less than 50 mol% of vinyl alcohol units Ethylene-vinyl alcohol co- and terpolymers, ethylene-mono-gasification master copolymer, polysulfonate, poly (alkylene oxide .. oxygen), such as poly (gasified propylene) or poly (ethylene oxide); benzene gas Resin, such as by the fermentation of natural gas, 5 | Cases of natural shell M added, ester f is difficult to gamble or as W The quality of the source, the P compound is combined with the lignin U compound, and the Wei-Jin-poly is the source of the Mt seeds of the celestial powder. This combination is like the quality of the f-polymer, which changes the -P permissible and physical ester. Extremely bright complex acid, hair polymerization or vinegar is the nature of elemental fiber texture. It is difficult for the succulent nails of Jiweiweiwei Department to form quality I. For example, the melt-modified sugar esters melted polyacid ethers should be shell vinegar or anti-polyacrylic acid, and the age-bearing carbendazim can be decoupled from the source. Sour and Coming, Ru Ding, printed by the Staff Consumption Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. This paper standard is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm). A6 B6 Printed by the Staff Consumption Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Preparation V. Description of the invention (7) can be about 10:95 to about 5:90, preferably about 60:95 to 5:40 for thermoplastic polar polymers, more preferably about 80:95 to about 5:20, to be useful polar polymers are aliphatic polyamides formed from internal amides, such as polycaprolactam, polyundecane amide, and polydodecane amide; by Biphenol A, poly (terephthalate) formed polyesters; and elastic polyurethanes, such as those with poly- or polyester-polyol fragments. Note the invention in detail BM; / Therefore, the present invention is a polymer blend, including: (a) from about 80 to about 95 parts of at least one polar polymer selected from poly (vinyl chloride), poly Sulfate, polyglutaraldehyde imine, methylmethacrylate polymer, polyamide, polyester, or polymer containing units derived from styrene and acrylonitrile; (b) from about 5 to about 20 parts of the polymer composite, including: (i) from about 60 to about 95 parts by weight of the first polymer containing at least 50 mole% of -CH2-CH- structural unit; I 0H (Π) from about 5 Up to about 40 parts by weight of the second polymer, which contains at least about 70 parts of units derived from at least one lower alkyl ester of methacrylic acid or acrylic acid, and at least one part of ethylene derived from containing amide groups Units based on vinyl or vinylene monomers, or up to 25 parts of units derived from unsaturated carboxylic acids or anhydrides. The invention also includes polymer blends, including: (a) from about 10 to about 95 parts of at least one Polar polymer; (Please read the precautions on the back before filling this page)-Pack.

、 1T The size of this paper is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 mm). 7 A6 B6 The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperative printed the 5 'invention description (8) (b) from about 5 to about 90 parts of the following polymer compound: U) from about 40 to about 95 parts of the first polymer containing at least 50 mole% of -CH2-CH- structural units; I 0H Ui) from about 5 to About 60 parts by weight of the second polymer, which contains at least about 70 parts of units derived from methacrylic acid or acrylic acid, and at least about 25 parts of ethylene derived from / containing fermented amino groups Units based on vinyl or vinylene monomers, or up to about 25 parts of units derived from unsaturated carboxylic acids or anhydrides, where polar polymers are natural and refractory to melting, such as starch, chitin, and dehulled Polysaccharide, lignin or lignocellulose; and the components (a), (b) (i) and (b) (ii) can be mixed at the same time. The present invention also includes polymer blends, including: (a) from about 25 to about 95 parts of at least one polar polymer; (b) from about 5 to about 75 parts of the following polymer compound: (i) From about 40 to about 95 parts by weight of a first polymer containing at least 50 mole% of -CH2-CH- structural units; I 0H (Π) from about 5 to about 60 parts by weight of a second polymer, which contains At least 70 parts of units derived from at least one methacrylic acid or lower alkyl ester of acrylic acid, and at least one part of units derived from vinyl or vinylidene monomers containing aldamine groups, or up to about 25 parts Units derived from unsaturated carboxylic acid or anhydride. The paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 mm). (Please read the notes on the back before writing this page) 307789 A6 B6 Economy Printed by the Ministry of Standards and Standards Bureau Staff Consumer Cooperative V. Invention description (θ): Among them, the polar polymer is polyurethane, such as elastic polyurethane, benzene resin, ethylene / monoxide copolymer, Modified ray of dimensional, such as weiwei ester, or poly (alkylene oxide). The present invention also includes all of the above blends, where the polymer composite includes: (i) from about 60 to about 95 parts by weight of the first polymerization containing -CH2-CH-, structural units containing at least 50 mole% I OH (M) from about 5 to about 40 parts by weight of a second polymer, which contains at least 70 parts derived from methylmethacrylate units, and at least about 25 parts derived from N-vinyl Units of pyrrolidone, or up to about 25 parts of units derived from methacrylic acid. Such blends can be in the state of extruded films, extruded sheets, extruded strands, or injected molded objects. Such blends can be prepared by the methods in which components (a), (b) (i) and (b) (ii) are essentially simultaneously combined. In the scope and description of the patent application, the total number of polar polymer parts and composite parts is 100 parts, and other substances may exist, as long as the polar polymer and the composite are within the defined range. Similarly, in the composite, the weight part of the vinyl alcohol polymer and acrylic acid mono- or terpolymer is 100 parts by weight, and other substances may be present as long as the vinyl alcohol and acrylic polymer are within the defined range. The composite may contain a blend of high molecular weight and low molecular weight vinyl alcohol polymers. This compound may contain a small amount of glycerin or other plasticizers. This compound may contain impact modifiers known in the art, such as poly (propylene (please read the precautions on the back before writing this page) 丨The size of the bound paper is in accordance with the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 9 A6 B6 Printed by the Employees Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

5. Description of the invention (10) Acid ester) The first stage or the first stage of polybutadiene and the second stage of methacrylate or styrene second stage, which may exist in the form of shells or separate regions in the core . Each stage may contain acid-functional groups. The blend can be prepared by dry blending the ingredients and melt processing in an extruder or hot mixer to form granules M, which can then be processed to the desired target, or the dry blend can be directly melted Processed into the final object. The blend may contain more than one type of polar polymer. The blend may further contain pigments, dyes, heat stabilizers, anti-gasification agents, lubricants, fillers, etc. When emulsion polymerization is a convenient way to prepare additive polymers (poly (vinyl alcohol) is pseudo-solid), and it is directly processed by removing water, such as extrusion in an emptying extruder, or by When the powder blend is dried under vacuum and then blended with the matrix polymer, the blend can be further prepared by mixing the additive polymer in an emulsion state. When the additive polymer is prepared by polymerization (but the poly (vinyl alcohol) and the matrix polymer are in solid state), and then directly processed by removing water, such as extrusion in an emptying extruder, or by vacuum When the powder blend is dried to form a blend, the blend can be prepared by mixing the additive polymer in an emulsion state. The term "a compound" is used in the specification and patent application, which means that the poly (vinyl alcohol) component and the acrylic copolymer additive component need not be blended together before being mixed with the polar polymer; one of the present inventions holds The objective can be described equally as a polymer blend comprising the following: U) from about 25 to about 95 parts of at least one polar polymer; (b) from about 2 to about 71.25 parts containing at least 50 mol%- CH2-CH- | 0H (Please read the precautions on the back before writing this page). Binding-Ordering. This paper size is applicable to China National Standards (CNS) A 4 specifications (210 X 297 mm) ι λ A6 Ministry of Economic Affairs Printed by the Central Standards Bureau employee consumer cooperative

___B6_ V. Description of the invention (11) The first polymer of the structural unit; (c) From about 0.25 to about 45 parts by weight of the second polymer, which contains at least about 70 parts of lower alkanes derived from methacrylic acid or acrylic acid Ester units, and at least one unit derived from vinyl or vinylidene monomers containing aldamine groups, or up to about 25 parts derived from unsaturated carboxylic acid or anhydride units. Therefore, the present invention intends to describe that the three components are mixed together at the same time, that is, essentially the same, and when the second (additive) polymer and the first polymer containing poly (vinyl alcohol) are combined first, It is then mixed with the matrix polymer. Since the present invention can provide poly (vinyl alcohol) incorporated into a polar polymer in a cost-effective manner without compromising the shielding properties, the resulting target is particularly useful for packaging that requires improved shielding properties, such as films, Flakes, bottles, etc. Such uses may include beverage bottles, food packaging films, etc. This blend can also be used for various molding or thermal forming objects that require both improved modulus and good processability. Such targets include toys, electrical equipment covers, etc. The melt blending of polymerase and polymer composites described herein can be made into films, film tubes, toys, pulleys, packaging, vents, curtain slides, door rollers, household containers, etc. The blend of the compound and the miscible and flexible elastic material can be used as a composition in contact with water and a rigid substrate, such as a modified wiper blade. Compound (or two separate components of the compound) or blended with environmentally degradable polymers, such as polylactate and other biologically-derived polyesters, or polyamide, or hydrolyzable, gasified or The paper standard for chemical modification of photolytically unstable units is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) i J (please read the precautions on the back before reading this page) --install. Order . A6 B6_ printed by the Employees ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of Invention (12) Ester, or light-sensitive additives, such as dibenzoyl. Such polymers may be included with caprolactone, oxalate or glycolide. Copolymerized and modified polycaprolactam; this polymer, especially when it is in the form of single fiber, thin rod, or mesh, will develop a higher amount in the environment when releasing poly (vinyl alcohol) The exposed surface, therefore, when exposed to the environment for a longer period of time, such as sunlight, rainwater, lake or seawater, compost, garbage heap, etc., it will degrade more quickly to depolymerize low molecular weight, more brittle, and lower formation retention polymerization, , Things. / The blend of the compound and the water-soluble or water-dispersible polyester can be used as a powder sizing aid for fabrics, which can be removed by washing at an appropriate time. Compounds combined with polar polymers with or without water-soluble electrolytes can be processed into flakes according to appropriate extraction techniques. The electrolyte and / or poly (vinyl alcohol) can be removed in the separation technique, leaving it useful Porous plastic H; can also be prepared with a porous structure for extraction and maintenance. This compound can be blended with an ethylene-vinyl alcohol copolymer and melt-processed as an adhesive resin composition or as a bonding layer having improved choking properties for compounding multi-layer bottles or packages. In the case where polar polymers can easily form fibers, the blend can be processed into a high-absorbency secondary dimension by melt extrusion technology. This blend can also be extruded and fiberized into a water-absorptive weave for use as a non-woven bonded substance. Such fibers or other extrudates, especially those made from polyamides that are biodegradable, can be used as components such as nets, monofilaments, diaper backings, floor coverings, etc. In the following examples, Xu describes the blending of melt-processable PVOH / acrylic acid co- and tri-polymer complexes with polar polymers (such as caprolactam). This paper scale is applicable to China National Standard (CNS) A4 specifications (210 X 2 mm) 1 9 (please read the precautions on the back and then write the clothing page)-installed, '1Τ, 307789 A6 B6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention Instructions (13) The physical and mechanical properties of several blends. The following abbreviations like the use of nylon * such as r polyamide, nylon 6 is polycaprolactam, PV0H is one or more specific polymers with vinyl alcohol units greater than 50 mol% in the examples. The substance " is one or more specific copolymers of alkyl methacrylate and vinyl lactam and / or copolymerizable acid. Example Bu 14 These examples illustrate the blending of a complex of poly (caprolactam) with high amine end content and AIRVOL®-205 / with a methyl methacrylate / N-vinylpyrrolidone copolymer , AIRVOL®-205 is hydrolyzed to Mwl3-50,000 of 88-89 ¾ vinyl alcohol poly (vinyl acetate) 〇Resistance 6 (XPN) obtained by Allied Signal is composed of 64.93meq amine end groups and 1.07meq acid The composition of the end groups, and the glass temperature Tg of the braided 6 (XPN) / PV0H-acrylic acid blend in Table I shows a single-line increase with the increase in the amount of the PV0H-acrylic acid composite. In Table I, it can also be observed that the melting temperature Tm and the fusion heat DHf both have similar opposite trends; the miscibility between the existing phases of these modified pseudo-blends in the thermal properties of the blend Ο The admixture mixture is fed into a single screw at 1 hour (25.4 mm), a hopper of an extruder of 2 4: 1 L: D, in which the mixture is melted and granulated; the processing conditions are as follows: extruder Barrel temperature: Zone-1 = 21〇υ Plaque field-2 = 210¾ Zone-3 = 213¾ Extruder die temperature: Die-1 = 216¾ Die-2 = 21610 Extruder screw speed: = 80rpm This paper size is suitable for China National Standard (CNS) Grade A 4 (210 X 297 mm) 13 (please read the precautions on the back before writing this page).-Pack ·, 1T. A6 __B6_ 5. Description of the invention (14) The tablets are dried and The thermodynamic stability and mixing properties were evaluated by DSC. As shown in Table I, the melt processable PVOH / acrylic acid compound can be mixed and miscible with Nylon 6 (XPN) under a P (MMA-NVP) acrylic copolymer in an amount of up to 70% by weight. It should be noted that all blends containing PV0H / acrylic composites can hold the high melting point of nylon 6 and are suitable for high temperature applications. In Example 13, a binary consisting of nylon 6 (XPN), AIRVOL® -205 and acrylic copolymer in a 3: 2 weight ratio, and a melt processable composition / material of P (MMA-NAP = 75/25) The blend, under the aforementioned processing conditions, is melt mixed, extruded and pelletized to produce a thermally stable blend. The thermal properties of the blends were evaluated by DSC and listed in Table I. (Please read the precautions on the back before writing this page) Binding-Order · * 'Printed by Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs

4 1X The size of this paper is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 mm) A6 B6 5. Invention description (15) (please read the precautions on the back first and then write this page) Table I: System Thermoplastic properties of medium homopolymers and blends: nylon 6 (XPN) / (AIRV0L®-205: P (MMA-HVP = 75/25) = 4: 1 numbered polymer / mixed compound ( w / w) Τκίΐη) TmfT!) DHfiJ / e) 1. Naibian-6 (XPH) 100 52.21 224.88 68.03 2. AIRV0L®-205: P (MMA-NVP) = 75/25) = 4: 1 100 68.75114 .33 182.62 24.01 3. AIRV0L®-205: P (MMA-NVP = 75/25) 3: 2 '100 4. Instance 1 / Instance 2 95/05 51.26 222.14 64.89 5. Instance 1 / Instance 2 90/10 53.24 222.11 60.83 6. Instance 1 / Instance 2 85/15 53.99 221.61 56.21 7. Instance 1 / Instance 2 80/20 55.02 221.12 46.25 8. Instance 1 / Instance 2 75/25 55.97 221.32 50.92 9. Instance 1 / Instance 2 70 / 30 60.16 221.37 45.05 10. Instance 1 / Instance 2 60/40 63.16 219.90 40.39 11. Instance 1 / Instance 2 50/50 64.38 218.91 35.84 12. Instance 1 / Instance 2 40/60 69.16 215.17 18.97 13. Instance 1 / Instance 2 30/70 73.47 219.65 15.58 14. Instance 1 / Instance 3 50/50 6 0.00 215.53 33.61 Printed paper size of the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A 4 specifications (210 Χ1397 mm) A6 ___B6_ V. Description of the invention (16) gm 15-17 By example Under the processing conditions described in 1, in a single-screw extruder, dry blending and melt mixing to prepare poly (caprolactam) (with about the same amount of acid and amine end groups with a molecular weight of about 18,000 resistant to 6 ( 06 ?! ^ 0 ^ 8202)) and AIRV0L ®-2 05 and acrylic acid copolymer P (MMA-NVP = 75/25) of the binary blend of the melt-processable composite. Granulate this extrudate and heat it in DSC

Before analysis, dry in forced air, oven, and injection mold on an A R B U R G injection molding machine equipped with heated ASTM / strip molds to form test pieces. The molding conditions were: nozzle: 2281; areas 1, 2 and 3: 223-230Ό; injection pressure: 3: lmpa; post-pressure: 2.1 mpa; molding temperature: 35C. The thermal and mechanical properties are shown in Table E and Table M, respectively; the PVOH-acrylic acid compound is incorporated into the nylon 6 phase, which has a slight impact on the impact and tensile properties of polycaprolactam. (Please read the precautions on the back before writing this page)-installed, this paper is printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The paper size is in accordance with the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 16 A6 B6 V. Description of the invention (17) Table I. Thermal properties of homopolymers and blends in the system: Kap 6 (CAPROH 8202) / AIRV0L®-205: P (MMA-NVP = 75/25) = 4: 1 ΜΜ. The polymer / composite component is iw / w) ΤκίΙη) ΤηιίΠΠ) 15. Kap-6 (CAPROH 8202) 100 54.25 223.96 70.97 16. Example 15 / Example 2 90/10 52.60 221.99 70.04 17. Example 15 / Example 2 80/20 54.18 222.33 61.06 Physical properties of blends in the table system: nylon 6 (CAPR0N 8202) / AIRV0L®-205: P (MMA-HVP = 75/25) = 4: 1 (please first Read the precautions on the back and write this page) Γ Examples Physical Properties Printed by Employees ’Consumer Cooperatives, Central Bureau of Standards, Ministry of Economics 15 16 17 Specific Gravity 1.136 1.148 1.158 Tension-generation, gPa 25.8 26.1 28.5 Elongation at break 2200 2200 2200 Tension- Modulus, mPa 1.15 1.27 1.32 Tensile impact strength (KJ / m2) 1232.25 1072.81 628.66 DYNATUP impact strength (J) 54.91 74.18 6.98 Ehrlich notch impact test at 0¾ (J / ra) 0.71 0.56 0.62 Ehrlich notch impact test at 23¾ (J / iii) 1.29 1.15 1.03 Ehrlich notched impact test at 231C 47.48 46.79 47.70 (J / m) (not cracked) Rockwell hardness (unrefined), L 88.05 92.35 93.80 Rockwell hardness (refined at 80C for 4 hours), L 93.30 95.80 DTUFL (264psi, 2C / min) 51.15 52.00 50.30 (unrefined) 0¾ DTUFL (264psi, ZO / iBin) 60.20 53.55 (at 80t: refining for 4 hours), CLASH-BERG torsional modulus, gPa, at 40¾ 0.83 0.67 0.67 .gPa, at 80 it 0.34 0.28 0.23 gPa, at 120Ρ 0.27 0.23 0.17 丨Install-, 1T.

C This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X mm) I ^ A6 B6 307789 5. Description of the invention (1 · 8) Example 1 8-3 5 These examples prove that acrylic terpolymer is The main blend of melt-processable compound and various polyaldehydes. Among the following blend compositions, the acrylic compound was studied as follows: (a) PV0H-1 is hydrolyzed to 87-89% w vinyl alcohol with a molecular weight of 13,000-50,000 and is known as AIRV0L®-205 (Air

Products Co. ,, Allentown, Pa) (Ethyl acetate) / Acrylic acid prepared and isolated from European Patent Application 91/3112652 and having composition P (MMA-HVP-MAA = 70/25/05) 4: 1 compound of terpolymer, where MMA is methyl methacrylate, NVP is N-vinylpyrrolidone, and MAA vulcanized methacrylic acid; (b) PV0H-2 pseudo-completely hydrolyzed PV0H (AIRV0L®- 107) (MW13,000 -50,000, degree of hydrolysis 98-98.8%) and acrylic acid trimer P (MMA-NVP-MAA = 70/25/05) 4: 1 complex. Nylon 6 (Example 15), Knitted 11 (polyundecane amide), Knitted 12 (polydodecane amide) and ready-to-be-transparent Nylon 12 (may contain other functionality to reduce The crystallinity and transparency of the polymer, under the trade name GriUmid TR 5 5 FC, supplied by EMS-American Grilon Inc., Sumter, SC, are in the K i 1 1 i ο n extruder, as previously prepared Prior to blending and melt mixing of the melt-processable PV0H compound, it is dried in a forced air oven at 75 =. For comparison purposes, each sample of nylon resin is also extruded and granulated in the same way, obtained from the compound and pure resin The pellets are then extruded and injection molded into films (3-5 mils) and ASTM parts. The gas permeability of the film is tested and the tension and impact properties of the parts are evaluated by the ASTM method. The size of this paper is in accordance with Chinese National Standard (CNS) A 4 specifications (210 297 mm) 1 8 (please read the precautions on the back before writing the clothing page). .1Τ. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs System I A6 B6_ printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (19) From the data in Table IV-VO, it can be seen that the 02 resistance of the braided / PVOH-acrylic acid terpolymer blend, At 80% relative humidity, it is 30 to 50% higher than that of pure nylon. When considering the harmful effects of moisture on the gas barrier properties of both nylon and PV0H, this improvement in the permeability of 02 is not meaningful; improvements can also be observed in the tensile properties of various nylon blends. However, all the knitting / PVOH-acrylic acid terpolymer blends show the loss of impact properties. The tension and impact properties of the blend of nylon and PV0H-1 and PV0H-2 can also be observed. This possibility may be explained by the improvement of physical properties, which may be -0H of PV0H and nylon -N- Intermolecular reaction between Η and -C = 0. hh ^ m 18-21 Nylon 6, Nylon 11, Knitted 12 and Holding Grade Transparent Nylon 12 (Grilamid TR55FC) samples are dried in a forced air oven at 75C, and then extruded to form a film (3- 5 mils) or injection molding on an Arburg injection molding machine, the film is extruded under the following processing conditions: Extruder barrel temperature: Zone-1 = 191.Ot: Zone-2 = 20 4. 4 ¾ Zone -3 = 204. Mold temperature: Mold-1 = 199.0¾ Speed: RPM = 55 Rolling temperature: 38.0¾ Injection molding conditions for nylon 6 and 11 are as follows: Nozzle = 234C; Zones 1, 2 and 3 = 222 respectively , 230 and 221C; injection pressure = 3.1 mPa; back pressure = 2.1 m Pa; molding temperature = 5 2 C. The difference in the molding conditions of nylon 12 is only at the above temperature • Nozzle = 2431; Zones 1, 2 and 3 = 240, 264 and 25710, respectively. List IV of gas permeability and organic maple properties. _ This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 19 (please read the precautions on the back before writing the clothing page) —installed-* π_ A6 B6 V. Description of invention (2¾ table IV. Examples of physical properties of nylon-6, -Π, -12 and Grilamid Physical properties Nylon 6 Nylon-11 Nylon-12 GRILAMI1 hh Comparative example 18 19 20 21 Tension-generation, mPa 31.7 10.5 27.3 68.5 When broken Elongation%, > 260 > 260 > 256 > 180 Tensile-Modulus, gPa 1.3 0.26 0.93 1.87 DYNATUP impact strength (J) 68.9 45.80 42.49 79.07 23¾ Ehrlich notch impact test (J / m) 139.37 Bending 46.46 18.69 DTUFL (264psi, 2 * G / min) (unrefined) ¾ 53,55 47.05 56.95 129.05 DTUFL (264psi, 2υ / πιίη) (at 80Ϊ: refining for 4 hours), υ 〇2 permeability, 80% RH 58.50 54.20 58.20 132.45 (approximately mil / lOOin2 · Atm, Day) 73.08 66.60 54.82 勇 例 "2 5 (please read the precautions on the back before writing the clothing page)-outfit-* 1T. Employee Consumer Cooperative of the Ministry of Economic Affairs Central Standards Bureau Print the PVOH and acrylic terpolymer P described in Example 4 (MMA-NVP-MAA = 70/25/05, molecular weight MW = 77000) Dry blended, extruded and granulated to obtain melt-processable PV0H compound. PV0H compound is mixed with nylon 6, nylon 11, nylon 12 and GRILAMID TR55FC to obtain nylon to melt-processable PV0H 4: 1 Proportion of the blend. This blend is evaluated for mechanical properties according to ASTM standards, and the properties are listed in Table V. This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) 20 A6 B6 V. Invention Description (21) The Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative Printed a Table V. Blending resistant and melt-processable PV0H (AIRV0L-205) / P (MMA-NVP-MAA = 7 0/25/0 5) blend The physical properties of Fenli 2JL 2 3 ZA ... 6% (w / .w) resistance: 80 resistance 11¾ (w / w) 80 resistance 12% (w / w) 80 G RIL A Μ ID% (w / w) 80 PV 0 Η-1% (w / w)! • • 20 20 20 20 Physical properties Tension-generation, mPa 56.79 26.77 40.58 75.99 Elongation at break,% 319.90 232.60 233.10 181.40 Tension-modulus, gP a 1.84 0.56 1.37 1.99 DRNATUP impact strength ⑴ 6.75 5.00 5.78 20.88 23 It's Ehrlich notch punch 58.21 34.71 22.96 13.35 impact test (J / m ) DTUFL (26 4 ps i, 2 / min) (unrefined) C 53.65 49.40 57.15 124.25 DTUFL (264psi, 2 V / min) (at 80 t: refining for 4 hours), V 58.10 49.80 62.25 124.30 (please read the back first Note: Please write this page again) Γ: .Installed. • 1T. This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) 9 1 A6 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs B6 5. Description of the invention (22) Examples 26-29 The melt-processable PVOH composite (PV0H-2) used in these examples is made of AIRV 0 L®-107 (Mw = 13-50K, and the degree of hydrolysis is equal to 98.0 To 98.8 ears? 0 and MMA / HVP / MAA = 70/25/05 composed of propionic acid trimer; this complex is described in Examples 18-35. The PVOH compound is prepared by melt mixing in a single screw extruder. After being in the form of pellets, the compound was mixed with all the knitting compounds (except Grilanid) of Examples 18-21, blended, blended, and extruded and granulated under the following conditions: Extruder barrel temperature: Zone-1 = 210¾ Zone-2 = 2 13 ls: Zone-3 = 212¾ Extruder die temperature: Die-1 = 206 ¾ Die-2 = 206¾ Extruder screw speed: = 100r > pn «in PVOH / Grilamid blend In this case, the extrusion process is carried out in barrels and dies at a higher temperature: zones -1, _2 and -3 are 221, 240 and 241, respectively; dies -1 and -2 are 232 and 221t, respectively. The extrudates were fed into a water bath and granulator. The extruded pellets were injection molded on an ARBURG injection molding machine and dried in a forced air oven 751. The weight percentage of the composition and its mechanical properties are summarized in Table VI. The impact value is tested according to ASTM D256-84 Ehrlich impact test method, the tension produces strength, the elongation and tensile modulus at break are tested according to ASTM D638-84; the drop weight impact is according to the procedure of ASTM D2444, with Dynatup impact Device measurement, the deformation temperature under load (DTUFL) you use ASTM D648 -7 2, to 0.25 inches (This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm> 2 2 (please read the back (Notes to fill out this page)

Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A6 ___B6_ V. Description of the invention (2》 6.3 5 m b) Thick test piece, measured under a load of 1.8 m Pa, in units. Table VI. Physical properties of blends of nylon and melt-processable PV0H (AIRV0L-107) / P (MMA-HVP-MAA = 70/25/05) 2A. ZJL 2Λ. 2_a. Nylon 6% (w / w): 80 nylon 11% (w / w) • 80 nylon 12% (w / w) • 1 80 GRILAM ID% (WW) · / 80 PVOH-2% (w / w): 20 20 20 20 Physical properties Tension-generating, mPa 45.52 10.45 29.78 69.43 Elongation at break,% 221.67 175.00 205.00 164.00 Tensile-modulus, gPa 1.95 0.44 1.23 2.37 DYNATUP impact strength (J) 10.27 2.88 9.04 9.27 23 its Einstein Notch impact test (J / m) 42.17 57.14 26.17 2 1.36 DTUFL (264psi, 2 t: / rain) (unrefined) 6 1.00 49.65 102.45 127.45 DTUFL (264psi, 2 V / min) (refined at 8〇υ for 4 hours ), &Quot; C 79.60 82.60 72.95 123.35 Example 3 Ο Ή The sample of the blend composition listed in Table VII was extruded into a film (3-5 mils) and a thick sheet (20-30 mils) in order to For extruding films and sheets, use a Killion extruder with 1 inch (25.4 mm), 24: 1 L / D and 3: 1 compression ratio. Installed on the extruder (please read the precautions on the back before writing the Zhu page) Γ. — Installed. * 1T. .Q. The paper size is applicable to China National Standard (CNS) Grade 4 (210 X 297 mm) 23 A6 B6 V. Description of the invention (2 4) Set a 6-inch (0.15 4 m) coating suspended flat film mold. The processing conditions are as follows: Extruder temperature zone-1 = 1 9 7 1C; zone-2 and -3 are 2 0 7 it, the screw speed is 55rpm, the film is squeezed to a cold roller maintained at 38¾, and drawn into 3 mils thick and wound at a speed of 30 feet per second (9.14 meters) on the roller. The gas permeability of the film was measured on the M0C0H Ox-Tran 1000 unit (manufactured by Hyundai Control Co., Ininneapolis, MN). Count / count in the diffusion cell and first pass nitrogen gas as the first step to establish the baseline, then expose the upper surface of the membrane to the atmosphere rich in gas and the lower surface to the carrier gas (1% H2 in N2) Middle), the nickel-cadmium fuel cell known as the Coalox detector tracks and detects the steady-state gas permeability. Install Ox-Tran 1 0 00 unit to record steady state flow, the unit is c.c.mil/100in2*Atin, Day. Measurements were made at 2 3 t, 0 and 80% relative humidity. The gas permeability was measured using A ST M test D-3 9 8 5. The measurement results are listed in Table VD. Table VII. Physical properties of blends of nylon and melt-processable PV0H (AIRV0L®-205) / P (MMA-NVP -MAA = 70/25/05)

(Please read the precautions on the back before writing this page. W Central Bureau of Standards, Ministry of Economic Affairs, Industry and Consumer Cooperation Du Dufen, ZSL 1L 12. H Μ. 2lL, nylon 11% (w / w): 90 70 resistant 12% (w / w): 90 70 GRILAMID% (w / w): 90 70 PV0H-1% (w / w): 10 30 10 30 10 30 Physical properties s 0 2 Permeability, 8 0% R. Η. 45.2 33.8 59.7 37.6 49.6 31 (cc.mi l / 100in2.Atm.Day) This paper scale applies the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 24 A6 __B6_ V. Description of the invention (2 Ling Examples 3fi-44 These examples demonstrate polyurethane modified with the aforementioned complex. The data obtained in Table VIII-X show that some of the polyurethane and PVOH-acrylic acid terpolymer complexes Degree of miscibility. Each polyurethane / PVOH-acrylic terpolymer blend is better than the other matrix polyurethane resins in showing better tension and gas permeability properties. Table IX and The blends of PV0H-1 and PV0H-2 / polycarbamate in X are comparable! Physical properties. It should be noted that both nylon and polyurethane can pass -0-H, -C = 0 -The N-H part undergoes hydrogen bonding reaction with PVOH-acrylic acid terpolymer. The tensile strength and high moisture permeability of nylon polyurethane are significantly improved, among which are the fiber-forming properties of these polymers Important meaning. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before writing this page) : 1 weight ratio, blended with three different thermoplastic polyurethane elastomers (PUE), the PUE used in the experiment is composed of polyisocyanate (aliphatic or aromatic) and polycool, polyether or polyhexyl It is composed of the reaction product of lactone polyol. In the preparation of PUE, chain extenders such as diols and diamines can be used. The specific PUEs used are obtained from Dow Chemical Company under the trade name Pellethane® (from 4,4′-Asia Methyl diphenyl diisocyanate, polyurethane obtained from 1,4-butanediol and polybutylene glycol) and available from BFGoodrich, under the trade name Estane® (derived from polyester polyol matrix Polyurethane). The mixture is fed with L / D = 24: l and compression ratio 3: 1 Before the single screw extruder, it is mixed in a polyethylene bag. The processing conditions are as follows: Extruder barrel temperature: Zone -1, -2 and -3 are 197, 207 and 207T, and the die temperature is 199 and 201t: , The screw speed is 100RPM, the extrudate is extruded to the water bath and the paper size is in accordance with the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 25 A6 ___B6_ printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Description of the invention (26) In the granulator. After the pellets are dried, they are injection molded on an Arburg injection molding machine equipped with heated ASTM molds to form test pieces. The molding conditions are as follows: nozzle: 223Ό; zones 1, 2 and 3 are 236 ^: , 247¾ and 226C; injection pressure 3.1mPa; back pressure 2.1iaPa; molding temperature 49 die. Samples of blends and individual homopolymers are also extruded into films (3-5 mils) and thick tablets (20-30 mils). For film extrusion, use 1 inch (25.4 mm), Killion extruder with 24: 1L / D and 3: 1 compression ratio. The extruder is equipped with a 6-inch coated flat film die. The processing conditions are as follows: extruder temperature zone-1 = 1 9 7 Ό; zone-2 and -3 傜 2 0 7 Ό; the screw speed is 5 5 rpm; the film is extruded to a cooling wave wheel maintained at 38¾, and Pulled to a thickness of 3 mils and wound onto the roller at a speed of 30 feet (9.14 meters) per second; speed. The membrane was tested for gas permeability on a MONOC Ox-Tran 1000 unit (manufactured by the modern control company of Minneapolis, MN). The membrane was counted in a diffusion cell. It was first introduced with nitrogen gas as the first step to establish a baseline. Next, the upper surface of the membrane is exposed to a gas-rich atmosphere, and the lower surface is exposed to a carrier gas (1% Η 2 in N 2), known as nickel cadmium known as C 〇u 1 ο X detector The fuel cell tracks and detects steady-state oxygen permeability. Install the Ox-Tran 1000 unit to record the steady state flow, the unit is ccmil / 100in2. Atm.Day, measured at 2 3 " C and 0 and 80% relative humidity, using AST M test D-3 9 8 5 Test the oxygen permeability. Test the impact value according to ASTM D2 5 6-8 4 Ehrlich Notch Impact Test Method. Test tensile strength according to ASTM D638-84, elongation at break and modulus of tension. Measured with the Dynatup impact device according to the procedure of ASTM D2444 (please read the precautions on the back before filling in this page) Binding-Order. Ηέ. This paper is also applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 26 307789 α6 Β6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. # 明明 （27) The amount of weight drop impact. Under the load of 1.8 mPa, using the method of ASTM D648-72, measure the deformation temperature (D T U.F L) of the 0.25 inch (6.35 mm) thick test piece under load, in terms of υ. Table VIII. Physical Properties of Thermoplastic Polyurethane Elastomer hh Age Example 2_β_ai 1L · PELLETHANE 2363-55D% (w / w) 100 ESTAHE 58 1 34% (w / w) 100 ESTAHE 58309-021¾. w / w) 100 Physical properties Tension-generated, mPa% elongation at break > 231.0 > 260.0 > 26 0. Tension-modulus, gPa 0.10 0.03 0.0 .2 permeability, 80% RH 96.40 264.60 22 2 .cc.mil / (100in2, Day.Atn) Table IX. Physical examples of blends of thermoplastic polyurethane elastomers and melt-processable P V0H (AIRV0L®-205) _acrylic terpolymers 3J_ 4JL PELLETHAHE 236 3 -55D% (w / w) 80 ESTANE 58134% (w / w) 80 ESTANE 5 8 3 0 9 -0 2 1% (w / w) 80 PV0H-1% (w / w) 20 20 20 Physical properties Tension-generation, mPa 5.5 2.1 2. Elongation at break% 2 28.0 > 260.0 > 26 0. Tension-modulus, gPa 0.21 0.08 0.0 2 permeability, 80% RH cc.mil / (100in2, Day.Atm) 90.90 191.24 183. This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) 27 (Please read the notes on the back before writing this page ) A6 B6 V. Description of the invention (2¾ Table X. Physical properties of blends of thermoplastic polyurethane elastomer and melt-addable PVOH (AIRVOL®-107) -acrylic acid terpolymer PELLETHANE 2363- 550¾ (w / w) ESTAHE 58 1 34% (v / w) ESTANE 58309-021 ^ (w / w) PVOH-2% (w / w) Physical properties Tension-generation, mPa elongation at break% Tension-mode Number, gPa 〇2 permeability, 80% RH cc.mil/(100in2, Day.Atn) 80 LA. 80 20 20 80 20 (please read the precautions on the back before writing the table page) Γ 6.7 3.3 > 216.0 > 260.0 0.22 0.07 > 260.0 0.06 119.60 174.07 195.44 These examples illustrate the compounding of poly (vinyl alcohol) and (meth) acrylate / copolymerizable cyclic aldamine / copolymerizable acid terpolymer It can improve the properties of polyesters and polyesters. hh Comparative Example 4R-46 The samples of PET and PC were dried in a forced air oven of 100¾, and then extruded into a film (3-5 mol) or flakes. The flakes were injection molded on an Arburg injection molding machine. The films are listed below Extrusion under processing conditions: .Package-* 11. C. ^-Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative Printed Extruder Barrel Temperature Mold Temperature: Rate: Rolling Temperature: Zone-1 = 23 8 t Zone-2 = 2 5 3 t: Area-3 = 2 5 4 " G Mold-1 = 254Ό RPM = 55 38 This paper scale is applicable to China National Standard (CNS) Grade 4 specifications (210 X 297 mm) 28 A6 B6 V. Invention Description (2 9) The injection molding conditions for both PET and PC are as follows: Nozzle temperature = 251T :; Zones 1, 2 and 3: 238, 279 and 271 respectively; "Injection pressure = 3.4mPa; After pressure = 1.8 mPa; molding temperature = 2710; mechanical property data are listed in Table XI. The blend described in Table XII was prepared by melt-mixing the melt-processable PVOH composite described in Examples 18-35 with PET and PC and extruding the mixture. The blend was prepared under the conditions described in Examples 45-46 Next, they are extruded and injection molded into films and ASTM parts, respectively. The gas permeability and mechanical properties are listed in Table XII. / The data shows that the modulus, elongation at break and DTUFL increase, however, when PV0H-1 and PV0H-2 are included in human PET and PC, notch impact and drop weight impact increase. Table XI: Physical properties of PET and PC (CD 2000) (please read the precautions on the back before writing this page)-Installed _ Printed Polymer PET PC (CD200 Comparative Example Ρ) Ε Τ% (w / W) 100 PC (CD2000)% (w / w) 100 Physical properties Tension-generation, mPa 57.99 59.30 Tension-modulus, gPa 2.28 2.22 Elongation at break% 235.00 89.70 DYNATUP impact strength (J) 66.20 73.34 23¾ Ehrlich notch impact test (J / m) 25.63 574.58 DTUFL (2 6 4ps i, 2 υ / ο i η) (unrefined) t 65.20 132.45 DTUFL (264psi, 21〇 / ηίη) (at 80 ^ Refining for 4 hours) t: 66.15 131.30 This paper scale is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 2 9, 1τ., Line · V. Description of invention (3〇) A6 B6 Table XII. Examples of physical properties of blends of PET and PC (CD2000) and melt-processable PV0H-1 and PV0H-2 composites PET% (w / w) 80 PC (CD2000)% (wr / W) 80 PV0H-1% (w / w) 20 20 PVOH-2% (w / w) 20 Physical properties Tension-generation, m Pa '60.40-60.79 Tension-modulus, g Pa 2.63 2.65 2.74% elongation at break 213.00 1.19 & 247.00 DYNATUP impact strength (J) 3.11 1.37 5.40 23¾ Ehrlich notch impact test (J / m) 14.42 10.15 19.76 DTUFL (26 4ps i, 2 l; / min ) (Unrefined) υ 6 1.40 115.25 71.45 DTUFL (264ps i, 2 " C / min) (refined at 8〇υ for 4 hours) 65.70 113.50 7 1.80 --------- T- — i-- -,-1.1 ------ Dressing ------ · 玎 ----- ά (Please read the precautions on the back before writing this page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example S0-5 1 This example illustrates the physical properties of a ternary blend containing corn starch to a binary w complex " containing acrylic acid copolymers with amide and acid functionality and poly (vinyl alcohol). In a high-strength mixing pan, put 75 parts of poly (vinyl alcohol) (88% hydrolyzed, obtained from Example 1 above), corn starch (10 parts) and 5 parts of acrylic trimer (MMA / N-vinylpyrrole) A mixture of ketone / methacrylic acid = 73/25/02) This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 30 3〇7789 A6 B6 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy 5. Description of the invention (31). A small amount (0.5%) of hindered phenol antioxidant is also added. The particles were heated at a stirring speed of 800-900rp and a constant temperature of 45 · 〇 for 10 minutes, and the free-flowing powder was collected in a polyethylene bag. The control group consisted of 85 parts PV0H and 15 parts acrylic acid trimer (without corn starch ) Prepared. The above mixture is fed into a single-spiral Kollion extruder, and at a screw speed of 80 rpm and a zone of 193¾ and die temperature, but the zone 1 of the extruder is 1801C, the melt is mixed and the granules are released. The pellets are forced It was dried in a hot air oven, and then molded on an Arburg injection molding machine equipped with an ASTH bar mold at a nozzle temperature of 200C and an area, an injection pressure of 6.2mPa and a pressure after 1.4. Example 50 Example 51 Tensile strength, mPa 79.3 ΝΑ elongation at break,% 81 ΝΑ tensile modulus, gPa 4.46 4.44 Ehrlich notch punching system test, J / m 21.4 10.7 DTUFL, V 62 66 NA = not seen At a slightly lower heat distortion temperature, the ternary blend has improved notch impact properties. Example R2 In a similar manner to Example 50, 65 parts (vinyl alcohol), 20 parts corn starch, 10 parts acrylic acid trimer (MMA / N-vinylpyrrolidone / ethyl acrylate / methacrylic acid = 55/25 / 18/02) and 5 parts of glycerin blended, extruded and molded. The size of this paper is in accordance with Chinese National Standard (CNS) Grade 4 (210 X 297 mm) 3 1 (please read the precautions on the back before filling in this page) .— Package-* 1T.

Claims (1)

Annual supplementary one s Attachment Economic Lang Central Standards Bureau S Industry and Welfare Committee M will print the first case. Please apply for this application. _ No. Fan 46 Li 71 Special 1 Please include the package 1, the content of the few to the combined Ϊ 5 9 to poly-0 species from a propionate A port δ) "poly-V-r group-i via i-pole, class 4 4, / ('Amine dihydrogen penta). Polyene, ethylated acid by double Alkyl propionate 2 November 9th, the self-contained shape-selection system is the ester carbon of the polymer, the polymer is ethylene dibutyl / purchase allyl and \-/ ester diacetic acid diphenyl pair / 1 polyamine glycosaminoglycan B to benzene 5 / Self- \ J / «1Λ Group of grouped materials SBA / IV Included inclusion compound compound 9 to Η Η c-ο% of the formula; Mo Wu J 5 gathers less than one element with the first element, the mono-structure weight is less than 70, the less ester to alkane has 4 elements, and 1 contains the following: the amount of the compound element is Μ 4 to 5 white * 1 « I acid allyl or acid allyl methyl esters are as little as possible-as few as 25 dianhydrides up to a single acid species or a single unit Ethylene sulfide and amines derived from the amines derived from the ethogenous compound of the ethogenous compound containing the white shengyan or the compound of the compound in the compounding of the compound 1ί The special enrollment of the fan: 申 quo 如 包 2 The formula ¾; the ears do n’t fit together ο 5 gather one to the first element of the first element I structure. 结 5 -9 Η C. To -ο 2 6 Η C Since I \ 1 / ♦ I to 5 Baishengzi Yan Yan 5 7 As little as the second part containing the compound ft * Up to 1 Species as little as Yuan Shan's allyl acrylic acid paper This paper standard is suitable for China National Standard (CNS) A4 specifications (210Χ 297 Public ») 1 307789 The employee of the Central Bureau of Standards of the Ministry of Economic Affairs of the Commission for the Profit and Welfare printed a unit derived from N-vinylpyrrolidone or up to 25 units derived from methacrylic acid. 3. If the blend of item 1 of the patent application is in the state of making a film, making a sheet, extruding a dimension or shooting a steamed article. 4. For example, the compound of item 1 of the scope of patent application, in which the components (a), (b) U) and b (i i) are mixed together at the same time. 5. A polymer blend, including: U) from 10 to 95 parts of at least one polar polymer; (b) from 5 to 90 parts of the polymer composite, including: i) from 40 to 95 weight 1 part of a first polymer containing at least 50 mol% of the structural unit of formula -CH2-CH-; I 0 Η ii) from 5 to 60 parts by weight of a second polymer containing at least 70 parts of a methyl group Units of acrylic acid or (^ -4 alkyl esters of acrylic acid, and at least one unit derived from amide-containing Z vinyl or vinylidene bodies, or up to 25 units derived from unsaturated carboxylic acid or anhydride Unit; one of the at least one polar polymer is selected from the group consisting of starch, dicetin, chitosan, lignin and androstin. 6. As described in the patent application item 5, the compound (A), (b) (i) and b (ii) are simultaneously mixed on this 難 霣. 7. A polymer blend, including: (a) from 25 parts to 95 parts of at least one polar polymer ; (B) From 5 to 75 parts of the polymer composite, including: i) from 40 to 95 parts of the paper size containing at least 500,000 ear% of this paper standard is applicable to China National Standards (CNS) A 4 specifications (210X297 company director)? 9Q778B ___H3__ formula -CH2! -J: H-the first polymer of the structural unit printed by the Miao Li concubine of the Central Standards Bureau of the Ministry of Economic Affairs; Ο Η ii) from 5 to 60 weight Parts of the second polymer, which contains at least 70 parts of units derived from at least one methacrylic acid or Ct-4 alkyl ester of acrylic acid, and at least one part of 25 parts derived from vinylamine or vinylidene group containing vinylamine groups Units with a single stern, or units with up to 25 parts of Z derived from unsaturated acid or anhydride; where the polar polymer is strong polyaminocarbamic acid_, phenoxy resin, containing less than 50 mol% ethylene fermentation units Ethylene-vinyl alcohol copolymer, ethylene / carbon monoxide comonomer, heterovitamin ester or poly (alkylene oxide). 8. The blend as claimed in item 5 or 7 of the patent application, wherein the polymer composite includes: i) the first from 40 to 95 parts by weight of Z containing at least 90 mol% of the structural unit of formula -CH2-CH- Polymer; up to 5 from Z part 5 7 to as few as 2 parts containing Λ3 5 of its compound up to I 5 0 2 1 up to or less than, and yuan Methyl acid allyl ethylene propylene H- group is derived from a derivative of acid, allyl methyl sulfonate, and is extruded 1. Image form. The shot item of the bark object compound is shot or the first item, Yuan Wei Fan Xianli is specially squeezed out, and the application is like 9 out of 5 and 5 parts into it, which is the same when the compound is mixed. 7 The first edition of this book is 1) and one * b) Please follow the standard of this paper as applicable to the national standard (CNS) A4 (210X297 public love)